CN102421824A - Liquid monobenzoxazine based resin system - Google Patents
Liquid monobenzoxazine based resin system Download PDFInfo
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- CN102421824A CN102421824A CN2010800205872A CN201080020587A CN102421824A CN 102421824 A CN102421824 A CN 102421824A CN 2010800205872 A CN2010800205872 A CN 2010800205872A CN 201080020587 A CN201080020587 A CN 201080020587A CN 102421824 A CN102421824 A CN 102421824A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The present invention provides a liquid resin system including a liquid monobenzoxazine monomer and a non-glycidyl epoxy compound, wherein the weight ratio of the monobenzoxazine monomer to the non-glycidyl epoxy compound is in a range of about 25:75 to about 60:40, The liquid resin system exhibits a low viscosity and exceptional stability over an extended period of time making its use in a variety of composite manufacturing methods highly advantageous.
Description
Cross-reference to related applications
The application requires to enjoy in the right of priority of the U.S. Patent Application Serial Number of submitting on May 14th, 2,009 61/178,188, and it is hereby incorporated by.
Federal government subsidizes the statement of research or exploitation
The present invention is so that United States Government supports to make under the contract number DE-FG36-07G017012 by granting in USDOE.Therefore, United States Government has certain right of the present invention.
Invention field
The present invention relates to high stability low viscosity resin system, it comprises liquid list benzoxazine (monobenzoxazine) resin and at least a non-glycidyl epoxy compounds.This resin system can be used as resin transfer moulding resin, vacuum-assisted resin transfer moulding resin, pultrusion resin, tackiness agent, prepreg resin or is used for other matrix materials when being used in combination when independent use or with other components makes type application.
Background of invention
Fibre-reinforced polymeric matrix composite material is used for many structure applications such as aircraft, space flight, automobile and sports goods are used.Usually, these high performance composite are included in solidified orientation successive thomel in the matrix resin.Glass or
fiber also can be used for these application.Although exist the matrix of many types of using in the matrix material application facet, epoxy resin owing to be easy to uses, excellent character and low relatively cost and in market, preponderate.
In recent years, because its fabulous physicomechanical properties and high thermal stability, the Polybenzoxazine resin has been used to produce high performance composite.Like US 4,607,091, US 5,152,993, US 5,266,695 be said with US 5,543,516, such Polybenzoxazine resin can be obtained by the reaction of polyphenol, formaldehyde and amine.A shortcoming of such Polybenzoxazine resin is that they at room temperature are solids, and when being used for making matrix material for example at resin transfer moulding (RTM) and vacuum-assisted resin transfer moulding (VaRTM), must be with they fusions.
In RTM and VaRTM, fiber preliminary working goods are placed in the airtight cavity mould with the shape manufacturing of the composite product of completion then.It is moistening and finally flood this preliminary working goods with originally then resin to be injected this mould.In RTM, resin is injected mould solidify then under pressure to produce matrix material.In VaRTM, the preliminary working goods are covered so that the preliminary working goods are sealed in the covering by the flexible sheet material or the wadding that are clipped on the mould.Then resin is introduced in the thin layer and be applied to covering inside to shrink flexible sheet material through vacuum pipe near the preliminary working goods and through this resin of preliminary working goods traction with moistening preliminary working goods and with vacuum.Receive at the same time under the vacuum, resin solidification.
Therefore, in RTM and VaRTM system, used resin must have extremely low complete wetting and the dipping of viscosity to allow the preliminary working goods that inject.In addition, this resin must keep such LV to be enough to be full of fully the time of this mould and these fiber preliminary working goods of dipping.At last, resin must be uniform before curing.These requirements have limited the utilization of Polybenzoxazine resin in RTM and VaTRM system, because in fusing down, they give the viscosity that is higher than requirement, comprise the solid of particle form and quick-recovery is solid-state soon under about 100 ℃ temperature being lower than very soon.
WO 2000/61650 has described by monohydric phenol, aldehyde and amine and has prepared the liquid benzoxazine colophony, and therein must be at room temperature applies the purposes in the application of benzoxazine colophony as liquid.Yet this liquid benzoxazine colophony still demonstrates and makes it in RTM and VaRTM system, use inconvenient viscosity and the short pot life that at room temperature is higher than requirement.
Summary of the invention
The invention provides liquid resin system, it comprises:
(a) the liquid list benzoxazine monomer of formula (I)
Wherein R is aliphatic series or aromatic base; And
(b) at least a non-glycidyl epoxy compounds, wherein component (a) arrived about 60: 40 scope to the weight ratio of component (b) at about 25: 75.
This liquid resin system demonstrates at room temperature less than the viscosity of 500cps and in the superior stability of the time that prolongs, makes that its use in RTM and VaRTM and other method for composite material is highly beneficial.
According to another specific embodiments, the present invention relates to a kind of method that is used for producing composite product in the resin transfer moulding system.This method comprises the steps: a) fiber preliminary working goods to be provided in the mould; B) liquid resin system of the present invention is injected this mould, c) make this liquid resin system flood these fiber preliminary working goods; And d) at least about 90 ℃ down the preliminary working goods of these resin impregnations of heating to be enough to produce the time of partly solidified at least solid articles.This partly solidified solid articles can carry out the after fixing operation to produce final composite product then.
In the alternate specific embodiments, the invention provides the method that in vacuum-assisted resin transfer moulding system, forms composite product.This method comprises the steps: a) in mould, to provide fiber preliminary working goods; B) liquid resin system of the present invention is injected mould; C) reduce pressure in mould; D) keep mould under approximately reducing pressure; E) make matrix resin flood these fiber preliminary working goods; And f) at least about 90 ℃ down the preliminary working goods of these resin impregnations of heating to be enough to produce the time of partly solidified at least solid articles.Solid articles that then can this is partly solidified carries out the after fixing operation to produce final composite product.
Invention specifies
Usually, the invention provides liquid resin system, it comprises: (a) liquid list benzoxazine monomer; And (b) at least a non-glycidyl epoxy compounds, wherein liquid list benzoxazine monomer (a) to the weight ratio of non-glycidyl epoxies (b) at about 25: 75 to about 60: 40 scope.Shockingly find; When preparing by this way; This liquid resin system at room temperature demonstrates the viscosity less than 500cps, makes it be highly suitable in the various process for producing composite materials that comprise RTM, VaRTM, pultrusion and long filament processing, producing high performance composite thus." room temperature " refers to about 20 ℃-25 ℃.In addition, found unexpectedly that liquid resin system demonstrates superior stability during storing the for some time that prolongs.Finally; Under solidifying; Liquid resin system provides has machinery and the fabulous equilibrated cured prod of chemical property, and described character comprises for example high glass transition temperature (Tg), decomposition temperature (Td), high tensile, low thermal coefficient of expansion and good snappiness.
Single benzoxazine monomer
Liquid resin system of the present invention comprises liquid list benzoxazine monomer.The term " single benzoxazine monomer " that place like this is used refers to the monomer that per molecule has a benzoxazinyl group.In addition, under the situation of " liquid list benzoxazine monomer " that uses a technical term, be to be understood that to using one or more liquid list benzoxazine monomers together.
Liquid list benzoxazine monomer can be represented by general formula (I)
Wherein R is aliphatic series or aromatic group.According to a specific embodiments, R is allyl group, do not replace or substituted phenyl, do not replace or substituted C
1-C
8Alkyl does not perhaps replace or substituted C
3-C
8Naphthenic base.Suitable substituents on the R-group comprises amino, C
1-C
4Alkyl and allyl group.Generally, one to four substituting group can be present in this substituted R-group.Preferred R is a phenyl.
Liquid list benzoxazine monomer can be by obtaining in the reaction that removes monobasic phenolic compound, aldehyde and primary amine under the situation of anhydrating.The monohydric phenol compound can be from about 1: 2 to about 1: 2.4 to the mol ratio of aldehyde, and preferably from about 1: 2.2 to about 1: 2.35, and phenolic compound can be from about 1: 1 to the mol ratio of primary amine reaction thing.
This monohydric phenol compound can have from 6 to 12 carbon atoms, 6 carbon atoms most preferably, and can be to replace or unsubstituted.Preferably, if when having substituting group, position between substituting group is in.The monohydric phenol examples for compounds comprise phenol ,-and right-cresylol ,-and right-ethylphenol ,-and right-isopropyl-phenol ,-and right-methoxyphenol ,-and right-thanatol ,-and right-isopropoxy phenol ,-and right-chlorophenol, 1-and beta naphthal and composition thereof.
Aldehyde can have from 1 to 6 carbon atom.Preferably, this aldehyde is formaldehyde, can be used as the Paraformaldehyde 96 acquisition that the aqueous solution or conduct are decomposed into formaldehyde.
The instance of primary amine comprises: the aromatic series list-or diamines, aliphatic amide, cycloaliphatic amines and heterocycle monoamine; For example aniline, neighbour-,-and p-phenylenediamine, p-diaminodiphenyl, 4,4 '-benzidine methane, hexahydroaniline, butylamine, methylamine, hexylamine, allylamine, chaff amine quadrol and tn.Amine can be at its carbon part separately by C
1-C
8Alkyl or allyl group replace.Preferred primary amine is according to general formula R
aNH
2, R wherein
aBe allyl group, unsubstituted or substituted phenyl, unsubstituted or substituted C
1-C
8Unsubstituted or the substituted C of alkyl
3-C
8Naphthenic base.At R
aSuitable substituents comprises amino, C on the group
1-C
4Alkyl and allyl group.Generally, one to four substituting group can be present in substituted R
aOn the group, preferred R
aIt is phenyl.Reaction times can vary widely with reactant concn, reactivity and temperature.For example, the reaction times can be from several minutes to several hours differences for solvent-free reaction, for example for diluting reaction 2 hours to 10 hours.If with formaldehyde based on the solution of water as this aldehyde, then can use the water miscibility organic solvent.If one or more reactants are liquid, can use it for other reactants (one or more) of dissolving.If all reactants all are solids, can be with they at first pre-mixing fusion or at first fusion pre-mixings then then.The temperature of reaction can be by normal experiment through calculating single benzoxazine and the product of not too hoping and optimizing then for the temperature and time of ideal product and confirm.According to a specific embodiments, temperature of reaction can be at about 0 ℃ to-250 ℃, and preferred about 50 ℃-150 ℃, and more preferably 80 ℃-120 ℃.Single benzoxazine building-up reactions can be carried out at normal atmosphere or under the pressure of about 100psi.According to another specific embodiments, this is reflected under the situation that has organic solvent and carries out.This organic solvent can be an aromatic solvent, for example toluene or YLENE, dioxane, ketone for example Virahol, sec-butyl alcohol or amylalcohol of methyl-isobutyl ketone or alcohol for example.This organic solvent can also be the mixture of organic solvent.
Non-glycidyl epoxy compounds
Liquid resin system of the present invention also comprises at least a non-glycidyl epoxy compounds.On this non-glycidyl epoxy compounds structure can be linear, branching or cyclic.For example, wherein can comprise one or more epoxy compoundss, wherein epoxide group forms the part of alicyclic ring or heterocyclic system.Comprising of other contains epoxy compounds, and it has at least a epoxy group(ing) cyclohexyl that is bonded to the group that contains at least one Siliciumatom directly or indirectly.Instance is disclosed in United States Patent(USP) No. 5,639, in 413, is introduced into as a reference.Still other comprises the epoxy compounds that comprises one or more cyclohexene oxide groups and the epoxide that comprises one or more cyclopentene oxide groups.
Especially suitable non-glycidyl epoxy compounds comprises the non-glycidyl epoxide compound of following difunctionality, and wherein epoxide group forms the part of alicyclic ring or heterocyclic system: two (2,3-epoxy group(ing) cyclopentyl) ether, 1; Two (2, the 3-epoxy group(ing) cyclopentyloxy) ethane, 3 ' of 2-, 4 '-epoxy group(ing) cyclohexyl-methyl-3; 4-epoxy-cyclohexane carboxylicesters, two (3,4-epoxy group(ing) cyclohexyl methyl) adipic acid ester, 3,4-epoxy-6-methyl cyclohexane ylmethyl 3; 4-epoxy-6-methylcyclohexanecarboxylic acid ester, two (3,4-epoxy group(ing) cyclohexyl methyl) hexane two acid esters, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) hexane two acid esters, ethylenebis (3; 4-epoxy-cyclohexane carboxylicesters), ethylene glycol bisthioglycolate (3,4-epoxy group(ing) cyclohexyl methyl) ether, VCH dioxide, Dicyclopentadiene (DCPD) diepoxide or 2-(3,4-epoxy group(ing) cyclohexyl-5; 5-spiral shell-3, the 4-epoxy group(ing)) hexanaphthene-1,3-dioxane and 2; 2 '-two (3, the 4-epoxycyclohexyl)-propane.
According to another specific embodiments, non-glycidyl epoxy compounds is to be selected from 3 ', 4 '-epoxycyclohexyl-methyl-3; 4-epoxycyclohexane carboxylate, 3,4-epoxycyclohexyl oxyethane, 2-(3 ', 4 '-epoxycyclohexyl)-5; 1 "-spiral shell-3 ", 4 "-epoxy cyclohexane-1,3-dioxane, VCH monoxide, 3; 4-epoxycyclohexane carboxylate methyl esters and two (3,4-epoxycyclohexyl methyl) adipic acid ester.
Liquid resin system of the present invention can prepare in known manner, for example through adopting conventional equipment such as stirred vessel, stirring rod, ball milling, sample mix device, static mixer or ribbon blender that component is mixed together.In a specific embodiments, with liquid resin system so that liquid list benzoxazine monomer is to prepare to about 60: 40 mode in about 25: 75 to the weight ratio of non-glycidyl epoxies.In another embodiment, with liquid resin system so that liquid list benzoxazine monomer is to prepare to about 57: 43 mode in about 35: 65 to the weight ratio of non-glycidyl epoxies.In another embodiment, with liquid resin system so that liquid list benzoxazine monomer is to prepare to about 55: 45 mode in about 45: 55 to the weight ratio of non-glycidyl epoxies.In another specific embodiments, the obtaining liq resin system makes that liquid list benzoxazine monomer is about 50: 50 to the weight ratio of non-glycidyl epoxies.After the preparation, can liquid resin system be packaged in the various containers like steel, tin, aluminium, plastics, glass or paperboard container.
Through in the temperature that is higher than 90 ℃, preferably, can obtain inflammable polymer resin from about 90 ℃ of thermofixation liquid resin system of the present invention under about 200 ℃ temperature.Therefore, according to another specific embodiments, liquid resin system of the present invention can itself as thermoset resin substrate or be used to prepare fire-retardant casting, prepreg, layer as the part of thermoset resin substrate and close product or injection system." fire-retardant " used herein refers to and meets UL94 standard specifications V0.
In a specific embodiments, with the part of liquid resin system of the present invention as thermoset resin substrate.This thermoset resin substrate can comprise the liquid resin system of the present invention at least about 30wt% based on the gross weight of thermoset resin substrate.In another embodiment, this thermoset resin substrate can comprise the liquid resin system of the present invention at least about 50wt% based on the gross weight of thermosetting resin mixture.In another specific embodiments still, this thermoset resin substrate can comprise the liquid resin system of the present invention of 70wt% at least based on the gross weight of thermosetting resin mixture.In addition, this thermoset resin substrate can comprise at least a in solvent, catalyzer, fire retardant and/or the filler.
Instance to the useful solvent of thermoset resin substrate comprises methylethylketone, acetone, N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, amylalcohol, butanols, dioxolane, Virahol, methoxypropanol, methoxy propyl alcohol acetic ester, N, glycol, ethyl glycol acetate, toluene and YLENE and composition thereof.This thermoset resin substrate can comprise the solvent of about 5wt%-30wt% based on the gross weight of thermoset resin substrate.
The instance that can be used for the catalyzer of thermoset resin substrate comprises thio-2 acid, phenol, sulfo-xenol benzoxazine, alkylsulfonyl benzoxazine, alkylsulfonyl and xenol.This thermoset resin substrate can comprise the catalyzer of about 0.001wt%-2wt% based on the gross weight of thermoset resin substrate.
The instance that can be used for the fire retardant of thermoset resin substrate comprises phosphorus fire retardant such as DOPO (9; The 10-dihydro-9-oxy phospho hetero phenanthrene-10-oxide compound of mixing),
PMP fire retardant (with the reactive organophosphorus additive of hydroxyl), CN2645A (, can obtain), Exolit fire retardant (can obtain), brominated polyphenylene support oxide compound and ferrocene from Clariant from Great Lakes Chemical Corp. based on phosphine oxide and the material that comprises phenol functional group in its end of the chain modification.Thermoset resin substrate can comprise the fire retardant of about 0.1wt%-50wt% based on the gross weight of thermoset resin substrate.
The instance that can be used for the filler of thermoset resin substrate comprises ammonium polyphosphate, softening agent, inorganic and organophosphorus compound, microvoid bulbus cordis and metal powder.This thermoset resin substrate can comprise the filler of about 0.001wt%-10wt% based on the gross weight of thermoset resin substrate.
Thermoset resin substrate for example can prepare through the various components of pre-mixing in known manner and mix these Preblendes then, perhaps through using conventional device that all components is mixed.
As stated, after the preparation, can with liquid resin system or thermoset resin substrate be applied on the base material and under at least 90 ℃ temperature, solidify to form the flame-proof composite material goods.Except RTM and VaRTM system; The additive method and the system that can liquid resin system and thermoset resin substrate be used for producing the flame-proof composite material goods comprise that the hot pressing of prepreg, sheet molding are compound, moulding, casting, pultrusion and long filament twine.
The character of flame-proof composite material goods can customize through adding fortifying fibre for some application.The instance of fortifying fibre comprises glass, quartz, carbon, aluminum oxide, pottery, metal, aromatic poly, natural fiber (for example flax, jute, sisal hemp, hemp fibre), paper, acrylic acid or the like and wynene and composition thereof.Fortifying fibre can for various forms of any, for example as the single thread that forms by parallel continuous fibre or at the discontinuous fibre (staple fibre) of a direction or rove, fabric such as Woven fabric or fabric, braid, unidirectional, two-way, random, quasi-isotropic or three-dimensional dispersive braided material, non-homogeneous network or mesh material and three-dimensional material like three Woven fabrics.
Therefore, according to another specific embodiments, a kind of method that is used for producing in the resin transfer moulding system flame-proof composite material goods is provided.This method comprises the steps: a) will comprise the fiber preliminary working goods introducing mould of fortifying fibre; B) liquid resin system of the present invention is injected mould, c) make liquid resin system flood these fiber preliminary working goods; And d) at least about 90 ℃, preferably under about 200 ℃ temperature, heats one section time enough of resin impregnation preliminary working goods to produce partly solidified at least solid articles at least about 90 ℃; And e) randomly make partly solidified solid articles carry out the after fixing operation to produce the flame-proof composite material goods.
In another embodiment, a kind of method that is used for producing in the resin transfer moulding system flame-proof composite material goods is provided.This method comprises the steps: a) will comprise the fiber preliminary working goods introducing mould of fortifying fibre; The thermoset resin substrate that b) will comprise liquid resin system of the present invention is injected mould, c) makes thermoset resin substrate flood these fiber preliminary working goods; And d) at least about 90 ℃, preferably under about 200 ℃ temperature, heats one section time enough of resin impregnation preliminary working goods to produce partly solidified at least solid articles at least about 90 ℃; And e) randomly make partly solidified solid articles carry out the after fixing operation to produce the flame-proof composite material goods.
In the alternate specific embodiments, the invention provides a kind of method that is used for forming the flame-proof composite material goods in vacuum-assisted resin transfer moulding system.This method comprises the steps: a) will comprise in the fiber preliminary working goods introducing mould of fortifying fibre; B) liquid resin system of the present invention is injected this mould; C) reduce pressure in mould; D) keep mould under approximately reducing pressure; E) make liquid resin system flood these fiber preliminary working goods; And f) at least about 90 ℃, preferably under about 200 ℃ temperature, heats one section time enough of these resin impregnation preliminary working goods to produce partly solidified at least solid articles at least about 90 ℃; And e) randomly make partly solidified at least solid articles carry out the after fixing operation to produce the flame-proof composite material goods.
In another specific embodiments still, the invention provides a kind of method that is used for forming the flame-proof composite material goods in vacuum-assisted resin transfer moulding system.This method comprises the steps: a) will comprise the fiber preliminary working goods introducing mould of fortifying fibre; The thermoset resin substrate that b) will comprise liquid resin system of the present invention is injected this mould; C) reduce the interior pressure of mould; D) keep mould under approximately reducing pressure; E) make this thermoset resin substrate flood these fiber preliminary working goods; And f) at least about 90 ℃, preferred at least 90 ℃ under about 200 ℃ temperature one section time enough of these resin impregnation preliminary working goods of heating to produce partly solidified at least solid articles; And e) randomly make partly solidified at least solid articles carry out the after fixing operation to produce the flame-proof composite material goods.
Liquid resin system of the present invention or thermoset resin substrate are particularly useful for the application of demanding thermostability, for example form as fuel cell composite product in, this fuel cell is used for the power supply at general-utility car, hybrid vehicle, canoe; Local on a small scale generating; Family's generating; The simple power supply that is used for isolated equipment such as spot camping is supplied with; And as the power supply supply that is used for satellite, space development and computer.
Therefore, in special specific embodiments, can be administered on the graphite liquid resin system or thermoset resin substrate and molded production fuel cell.For example the metal-salt of POLISHING WAX-103, fatty ester, Triple Pressed Stearic Acid or nonacosanoic acid mixes in mixing tank, mediates and or injection-molded, transfer mould or suppress moulding to produce fuel cell with graphite, liquid resin system or thermoset resin substrate and optional releasing agent.
In another specific embodiments still; When solidifying; This liquid resin system or thermoset resin substrate provide to be had greater than 120 ℃, is preferably greater than 160 ℃, most preferably greater than 200 ℃ and the solidified composite product that especially is preferably greater than 230 ℃ second-order transition temperature.
Embodiment
Liquid list benzoxazine is by the prepared in reaction of phenol, formaldehyde and aniline.Then will resin system 1 according to the present invention, liquid list benzoxazine and cycloaliphatic epoxy resin prepare through being mixed to about 55: 45 weight ratio with about 45: 55.Then with resin system 1 and only comprise the time that the resin system 2 of the comparison of liquid list benzoxazine is at room temperature stored an elongated segment.Initial for the test of every kind of resin system then and viscosity 1 month time the, 200 ℃ gel time and beginning temperature of reaction (onset temperature), the result is presented in the following table 1.
Table 1
| Character | Resin system 1 | Comparison tree resin system 2 |
| Initial viscosity at room temperature (cps) | ?381 | ?4500 |
| 1 month viscosity (cps) at room temperature | ?434 | ?115,000 |
| At 200 ℃ of initial gel times (sec) | ?583 | ?712 |
| 1 month gel time (sec) 200 ℃ of temperature | ?1180 | ?661 |
| The temperature that initially begins to react (℃) | ?222 | ?179 |
| 1 month beginning temperature of reaction (℃) | ?226 | ?176 |
Casting resin system 1 and solidified 2 hours down also at 200 ℃.The solidified product demonstrates by DSC, 164 ℃ and by TMA, 171 ℃ second-order transition temperature.
Although all specific embodiments of preparation of the present invention and use are described in detail in the above, should be understood that, the invention provides and can be included in wide in range various concrete inventive concept many applicatory hereinafter.Concrete embodiment as herein described only illustrates manufacturing and uses concrete mode of the present invention, does not limit the scope of the invention.
Claims (16)
1. liquid resin system comprises:
(a) the liquid list benzoxazine monomer of formula (I)
Wherein R is allyl group, unsubstituted or substituted phenyl, unsubstituted or substituted C
1-C
8Alkyl, unsubstituted or substituted C
3-C
8Naphthenic base; And
(b) at least a non-glycidyl epoxy compounds,
Wherein component (a) arrived about 60: 40 scope to the weight ratio of component (b) at about 25: 75.
2. according to the liquid resin system of claim 1, wherein R is a phenyl.
3. according to the liquid resin system of claim 1, wherein this non-glycidyl epoxy compounds is an alicyclic epoxide compound.
4. according to the liquid resin system of claim 3, wherein alicyclic epoxide compound is selected from 3 ', 4 '-epoxy group(ing) cyclohexyl-methyl-3; 4-epoxy-cyclohexane carboxylicesters, 3,4-epoxy group(ing) cyclohexyl ring oxidative ethane, 2-(3 ', 4 '-epoxy group(ing) cyclohexyl)-5; 1 "-spiral shell-3 ", 4 "-epoxy-cyclohexane-1,3-dioxane, VCH list oxide compound, 3; 4-epoxy-cyclohexane carboxylicesters methyl esters and two (3,4-epoxy group(ing) cyclohexyl methyl) adipic acid ester.
5. according to the liquid resin system of claim 1, wherein component (a) is in about 50: 50 scope to the weight ratio of component (b).
6. according to the liquid resin system of claim 1, wherein the viscosity of this liquid resin system is at room temperature less than 500cps.
7. in the resin transfer moulding system, produce the method for fire-retardant composite product, comprising: the fiber preliminary working goods that a) will comprise fortifying fibre are introduced mould; B) will comprise according to the thermoset resin substrate of the liquid resin system of claim 1 and inject mould, c) make these thermoset resin substrate impregnation of fibers preliminary working goods; And d) under at least 90 ℃ temperature, heats this resin impregnation preliminary working goods for some time to produce partly solidified at least solid articles; And e) randomly make partly solidified solid articles carry out the after fixing operation to produce the flame-proof composite material goods.
8. be used for forming the method for flame-proof composite material goods, comprise the fiber preliminary working goods introducing mould that a) will comprise fortifying fibre in vacuum-assisted resin transfer moulding system; B) will comprise according to the thermoset resin substrate of the liquid resin system of claim 1 and inject this mould; C) reduce pressure in this mould; D) keep this mould under approximately reducing pressure; E) make this thermoset resin substrate flood these fiber preliminary working goods; And f) under at least about 90 ℃ temperature, heats resin impregnation preliminary working goods for some time to produce partly solidified at least solid articles; And e) randomly make partly solidified at least solid articles carry out the after fixing operation to produce the flame-proof composite material goods.
9. the method for preparing the flame-proof composite material goods is included in and is higher than that thermofixation comprises the thermosetting resin mixture according to the liquid resin system of claim 1 under about 90 ℃ temperature.
10. according to the flame-proof composite material goods of the method for claim 9 preparation.
11. based on the gross weight of thermoset resin substrate comprise 30wt% at least according to the liquid resin system of claim 1 and at least a thermoset resin substrate in solvent, catalyzer, fire retardant and/or the filler.
12. liquid resin system comprises:
(a) the liquid list benzoxazine monomer that obtains of the reaction through monohydric phenol compound, aldehyde and primary amine, wherein the monohydric phenol compound is about 1: 22 to about 1: 2.35 and monohydric phenol compound to the mol ratio of primary amine for from about 1: 1 to the mol ratio of aldehyde;
(b) at least a non-glycidyl epoxy compounds
Wherein component (a) arrived about 60: 40 scope to the weight ratio of component (b) at about 25: 75.
13. according to the liquid resin system of claim 12, wherein this monohydric phenol compound be phenol ,-and right-cresylol ,-and right-ethylphenol ,-and right-isopropyl-phenol ,-and right-methoxyphenol ,-and right-thanatol ,-and right-isopropoxy phenol ,-and right-chlorophenol, 1-and beta naphthal or its mixture.
14. according to the liquid resin system of claim 13, wherein primary amine is formula R
aNH
2Amine, R wherein
aBe allyl group, unsubstituted or substituted phenyl, unsubstituted or substituted C
1-C
8Unsubstituted or the substituted C of alkyl
3-C
8Naphthenic base.
15. according to the liquid resin system of claim 12, wherein this is reflected under the organic solvent existence and carries out.
16. according to the liquid resin system of claim 15, wherein this organic solvent is toluene, YLENE, dioxane, methyl-isobutyl ketone, Virahol, sec-butyl alcohol or amylalcohol.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17818809P | 2009-05-14 | 2009-05-14 | |
| US61/178,188 | 2009-05-14 | ||
| PCT/US2010/034900 WO2010132772A1 (en) | 2009-05-14 | 2010-05-14 | Liquid monobenzoxazine based resin system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102421824A true CN102421824A (en) | 2012-04-18 |
| CN102421824B CN102421824B (en) | 2014-06-25 |
Family
ID=43085345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080020587.2A Expired - Fee Related CN102421824B (en) | 2009-05-14 | 2010-05-14 | Liquid monobenzoxazine based resin system |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US8853302B2 (en) |
| EP (1) | EP2430072B1 (en) |
| JP (2) | JP5837872B2 (en) |
| KR (1) | KR101739785B1 (en) |
| CN (1) | CN102421824B (en) |
| ES (1) | ES2502536T3 (en) |
| TW (1) | TWI540159B (en) |
| WO (1) | WO2010132772A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106995582A (en) * | 2017-05-16 | 2017-08-01 | 江苏恒神股份有限公司 | A kind of curable resin composition and its application containing benzoxazine and epoxy resin blend |
| TWI762483B (en) * | 2016-04-28 | 2022-05-01 | 日商Ｊｘｔｇ能源股份有限公司 | Composition for curing resin and cured product thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101844753B1 (en) * | 2010-08-25 | 2018-04-03 | 헌츠만 어드밴스드 머티리얼스 아메리카스 엘엘씨 | Formulated benzoxazine based system for transportation applications |
| EP2834308B1 (en) | 2012-06-27 | 2018-04-18 | Toray Industries, Inc. | Benzoxazine resin composition, prepreg, and fiber-reinforced composite material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5021484A (en) * | 1988-07-18 | 1991-06-04 | Gurit-Essex Ag | Fire retardant curable 1-oxa-3-aza tetraline (also termed "3,4-dihydro-1,3-benzoxazine") derived resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3433851A1 (en) * | 1984-09-14 | 1986-03-27 | Gurit-Essex, Freienbach | CHEMICALLY CURABLE RESINS FROM COMPOUNDS CONTAINING 1-OXA-3-AZA-TETRALINE GROUPS AND CYCLOALIPHATIC EPOXY RESINS, METHOD FOR THE PRODUCTION AND CURING THEREOF AND THE USE OF SUCH RESINS |
| EP0493310A1 (en) * | 1990-12-21 | 1992-07-01 | Gurit-Essex AG | Curable resin compositions having flame resistant properties in the cured state and use thereof |
| WO2000061650A1 (en) * | 1999-04-14 | 2000-10-19 | Edison Polymer Innovation Corporation | Development of low viscosity benzoxazine resins |
| JP2001278954A (en) * | 2000-03-29 | 2001-10-10 | Sumikin Chemical Co Ltd | Hardening agent for epoxy resin and composition for semiconductor sealing using the same |
| JP2003020410A (en) * | 2001-07-10 | 2003-01-24 | Toray Ind Inc | Resin composition for fiber-reinforced composite material and fiber-reinforced composite material |
| US6743852B2 (en) * | 2001-11-13 | 2004-06-01 | Henkel Corporation | Benzoxazines, thermosetting resins comprised thereof, and methods for use thereof |
| JP4333178B2 (en) * | 2003-03-26 | 2009-09-16 | 東レ株式会社 | Manufacturing method of fiber reinforced composite material |
| JP4661108B2 (en) * | 2004-07-05 | 2011-03-30 | 日立化成工業株式会社 | Liquid epoxy resin composition for sealing and electronic component device |
| JP5042491B2 (en) * | 2005-12-14 | 2012-10-03 | 株式会社ダイセル | Method for producing alicyclic epoxy compound and alicyclic epoxy compound |
| JP5135951B2 (en) * | 2007-08-27 | 2013-02-06 | Ｄｉｃ株式会社 | Epoxy resin composition, cured product thereof, and novel epoxy resin |
| JP5176075B2 (en) * | 2007-08-29 | 2013-04-03 | 日立化成株式会社 | Epoxy resin molding material for sealing and electronic component device provided with element sealed using the same |
| JP2009097013A (en) * | 2007-09-27 | 2009-05-07 | Hitachi Chem Co Ltd | Liquid resin composition for sealing, electronic component device and wafer level chip-size package |
| JP2009079015A (en) * | 2007-09-27 | 2009-04-16 | Idemitsu Kosan Co Ltd | Adamantane-containing epoxy compound, method for producing the same and epoxy composition |
-
2010
- 2010-05-14 ES ES10775597.7T patent/ES2502536T3/en active Active
- 2010-05-14 EP EP10775597.7A patent/EP2430072B1/en not_active Not-in-force
- 2010-05-14 US US13/266,476 patent/US8853302B2/en not_active Expired - Fee Related
- 2010-05-14 WO PCT/US2010/034900 patent/WO2010132772A1/en active Application Filing
- 2010-05-14 TW TW099115570A patent/TWI540159B/en not_active IP Right Cessation
- 2010-05-14 CN CN201080020587.2A patent/CN102421824B/en not_active Expired - Fee Related
- 2010-05-14 JP JP2012511042A patent/JP5837872B2/en not_active Expired - Fee Related
- 2010-05-14 KR KR1020117029834A patent/KR101739785B1/en active IP Right Grant
-
2015
- 2015-09-28 JP JP2015189815A patent/JP2016028156A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5021484A (en) * | 1988-07-18 | 1991-06-04 | Gurit-Essex Ag | Fire retardant curable 1-oxa-3-aza tetraline (also termed "3,4-dihydro-1,3-benzoxazine") derived resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI762483B (en) * | 2016-04-28 | 2022-05-01 | 日商Ｊｘｔｇ能源股份有限公司 | Composition for curing resin and cured product thereof |
| CN106995582A (en) * | 2017-05-16 | 2017-08-01 | 江苏恒神股份有限公司 | A kind of curable resin composition and its application containing benzoxazine and epoxy resin blend |
Also Published As
| Publication number | Publication date |
|---|---|
| US20120046388A1 (en) | 2012-02-23 |
| KR20120059455A (en) | 2012-06-08 |
| CN102421824B (en) | 2014-06-25 |
| EP2430072A1 (en) | 2012-03-21 |
| ES2502536T3 (en) | 2014-10-03 |
| EP2430072A4 (en) | 2012-11-28 |
| US8853302B2 (en) | 2014-10-07 |
| TWI540159B (en) | 2016-07-01 |
| TW201105725A (en) | 2011-02-16 |
| KR101739785B1 (en) | 2017-05-25 |
| EP2430072B1 (en) | 2014-07-16 |
| JP5837872B2 (en) | 2015-12-24 |
| JP2016028156A (en) | 2016-02-25 |
| WO2010132772A1 (en) | 2010-11-18 |
| JP2012526911A (en) | 2012-11-01 |
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